Black sulfur dye and process of making same.



- UNITED STATES PATENT OFFICE.

JULIUS ABEL, oF MANNHEIM, AND FRITZ KALKOW, oF'LUDwIesHAFEN,

. GERMANY, ASSIGNORS TO BADISOHE ANILIN & SODA FABRIK,

WIGSHAFEN, GERMANY, A CORPORATION OF BADEN.

AT LUD- BLACK SULFUR DYE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 692,174, dated January 28, 1902.

Application filed November 1, 1901.

. IO Germany, have invented new and useful improvements in Black Ooloring-Matterand Processes of Producing the Same, of which the following is a specification.

In the specification of Letters Patent No.

610,541 is described a blue-black dyestuff whichis obtained by heating para-hydroxyortho-para-dinitro-diphenylamin with sulfur and alkaline sulfids. We have nowdiscovered that an entirely-different coloring-mat- 1 2o ter is produced if the said hydroxy-dinitrodiphenylamin be melted with an alkaline sulfid and sulfur, or, what is equivalent. for this invention, with caustic alkali and sulfur in the presence of copper (either in the form of its salts or in the finely-divided state) at a suitable temperature. A coloring-matter is thus obtained which dyes cotton direct deep black or greenish-black shades which are exceedingly fast towashing even without aftertreatment with bichromates and the like. If

the dyeings obtained by means of the blueblack dyestuit produced according to the aforesaid specification, No. 610,441, be .subsequently treated with copper salts on the fiber the resulting coloring-matter becomes essentially bluer, while our new product by this treatment becomes a less greenish black; Further, on treating the dyeings obtained by means of the new coloring-matter produced 0 according to this invention with hydrogen peroxid they do not become blue, but dull blue-black. The dyestuif of the aforesaid specification, No.610,541, dissolves in alcohol, the solution being green; but the dyestufi 5produced according to this invention-is almost insoluble in alcohol. I

The following examples will serve to further illustratejthe nature of our invention and the manner in which the same may be three (3) hours.

Serial No. 80,798- (No specimens.)

carried into practical effect, but the invention is not confined to these examples. The parts are by weight.

Example 1: Into a solution of forty-six (46) parts of caustic soda and forty-two (42) parts of sulfur in forty-one (41) parts of water gradually introduce at a temperature of one hundred (100) to one hundred and ten (110) degrees centigrade thirty (30) parts of parahydroxy-ortho-para-dinitro-diphenylamin simultaneously with a solution of eleven (11) parts of copper sulfate in seventy-two (72) parts of water. Heat and stir the mass until it becomes of a thick consistency, and then gradually raise the temperature to two hundred and twenty (220) degrees centigrade and continue heating until the mass is dry. When powdered, the melt can be directly employed for dyeing. It dissolves in water, the solution being deep blue. It (lies cotton black.

Example 2: Gradually introduce into a solution of sixty(60) parts of sulfurin onehundred and fifty (150) parts of crystallized sodium sulfid at a temperature of about one hundred and ten (110) degrees centigrade thirty (30) parts of para-hydroxy-ortho-paradinitro-diphenylamin and at the same time a solution of twelve (12) parts of copper sulfate in ninety (90) parts of water. Slowly heat to a temperature of about one hundred and forty (140) degrees centigrade until the mass becomes dry, and then raise the temperature to about two hundred (200) degrees centigrade and maintain this heat for about The dyestufi produced can. be directly employed for dyeing and is very 8 similar to that of Example 1.

In the above example the twelve (12) parts of copper sulfate can be replaced by about three or four partsof finely-divided metallic copper. I I

Now what we claim is- 1. The manufacture of black coloring-matter by heating orthoepara-dinitro-para-hydroxy-diphenylamin with sulfur, an alkaline sulfid, and copper, substantially as described. 9 5

2. The new black coloring-matter containing sulfur such as can be obtained by melting ortho para dinitro para-hydroxy-diphenyl- 'amin with sulfur, sodium sulfid and copper In testimony whereof We have hereunto set I sulfate, which is almost insoluble in alcohol our hands in the presence of two subscribing 10 and dyes cotton, direct, deep black, to green- Witnesses.

ish-blaok, shades, which shades on treatment JULIUS ABEL. on the fiber with copper sulfate become but FRITZ KALKOVV. less greenish black,vand on treatment with Witnesses:

hydrogen peroxid do not become blue but ERNEST F. EHRHARDT,

dull blue-black, substantially as described. J ACOB ADRIAN. 

